... Title : ABSOLUTE RATE CONSTANTS FOR HYDROCARBON OXIDATION. XII. RATE CONSTANTS FOR SECONDARY PEROXY RADICALS,. ...

... Accession Number : AD0751310. Title : The Absolute Measurement of Rate Constants for Some Kay Reactions Involving Free Radicals. ...

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene

A method for the production of t-butoxy radicals by the photolysis of t-butyl hypochlorite was employed to determine the absolute rate of combination of t-butoxy radicals at room temperature and to determine the absolute rate of hydrogen atom abstraction ...

A new scheme for relating the absolute value for the kinetic rate constant k to the thermodynamic constant Kp is developed for gases. In this report the forward and reverse rate constants are individually related to the thermodynamic data. The kinetic rat...

... Abstract : The four propagation and three termination rate constants for the co-oxidation of cumene and Tetralin were determined at 30C and 56C. ...

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has

Absolute rate constants were measured for the reactions of cumylperoxy radicals with a number of hydrocarbons. The cumylperoxy radicals were produced from cumene hydroperoxide. Sufficient hydroperoxide was present to ensure that only cumylperoxy radicals ...

The equilibrium constants for the formation of some t-alkyl tetroxides and the rate constants for irreversible decay of the tetroxides have been measured by electron spin resonance spectroscopy at low temperatures. The equilibrium constant appears to be v...

... compounds, Fluorides, Molecule molecule interactions, Constants, Resonance, Infrared radiation, Ultraviolet radiation, Measurement, Reprints. ...

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using

... antioxidant properties. Kinetic solvent effects were observed. The reactivity of synthetic melanin, assessed through the quenching rate ... on the direct spectroscopic determination of their absolute reac...

The authors report absolute removal rate constants for silylene by reaction with alkanes, olefins, 1,3-butadiene, and acetylene at ambient temperature and 5-Torr total pressure. Rate constants were determined by laser resonance absorption flash kinetic spectroscopy. The results show that ...

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400

The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPz. In all cases the observed rate constants were found to increase with increasing ...

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At ea...

... a boost by the adaptation of the Low Altitude Plume Predictor ... Absolute Rate Constant for the Reaction 0 + NaO * Na + 02 by ... 1 HQ DA DAMA-ART ...

The absolute values of the second-order rate constants for the reactions of ozone with chloroethylenes and allyl chloride were determined in carbon tetrachloride solution at room temperature. The rate of ozone attack decreases strongly as the number of ch...

In this study, both relative rate and absolute kinetic measurements were made at 298 K for the reaction of chlorine atoms with the Cl-C4 alkanes. The relative rate studies were carried out using two different reaction chambers and GC to follow the loss of the organics upon reaction with atomic chlorine generated from the photolysis of ...

A general method for the measurement of absolute rate constants for the termination of photochemically produced organic free radicals in solution has been developed. Radicals are generated in the cavity of an EPR spectrometer by high intensity uv irradiat...

The absolute rate constant for the reaction of ground state oxygen atoms with methyl radicals is reported. The methyl radicals were generated by the reaction of oxygen atoms with ethylene in a fast flow reactor, and were detected by a photoionization mass...

Department of Materials Science and Metallurgy Pembroke Street, Cambridge CB2 3QZ A dissertation submitted. Sourmail in the Department of Materials Science and Metallurgy, University of Cambridge, between May 2003 energy for self-diffusion in iron r Constant R Gas constant t Time T Absolute temperature Tm Absolute

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF30CF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate consta...

... Title : Absolute Determination of Elastic Constants and Stresses from Ultrasonic Group Velocity Data,. Corporate Author : ...

Absolute rate constants for the copolymerization of alpha-methylstyrene and oxygen have been measured from 13 to 50 C. Experiments with 2,6-di-t-butyl-4-methylphenol at 65 C have shown that C6H5C(CH3):CH2 and C6H5C(CD3): CD2 have the same propagation rate...

Progress has been made in several areas of experimental and theoretical importance to the understanding of rate parameters in reactions important to combustion. We combined simple physical models with experiments devised to test these models with the objective of increasing our ability to estimate rate constants with an accuracy useful ...

Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0...

Electron transport parameters for gaseous mixtures containing electro-negative gases in buffer gases were investigated in this research program. Absolute electron attachment rate constants and cross sections of halogen compounds were measured. Photodetach...

We have used nuclear parity-changing collisions to obtain absolute level-to-level rate constants for reactive scattering in a triatomic system with identical nuclei. We have determined rate constants for the system (7)Li(2) (*)(A (1)Sigma(u) (+))(v(i)=2,j(i)=19)+(7)Li-->(7)Li+(7)Li(2) (*)(A ...

In the microscopic approach the decay constant of cluster radioactivity is determined by the preformation probability for the open channel multiplied with the Gamov penetrability. The preformation probability is found to possess a simple mass dependence on the emitted cluster. This observation leads to a formula for order-of-magnitude estimates of absolute ...

Laser flash photolysis studies of the reaction of benzylbromocarbene with pyridine enables the determination of the absolute rate constant for the 1,2-hydrogen migration in benzylbromocarbene. Thus, k = 5.6 {times} 10{sup 7}/s{sup {minus}1} at 25{degree}C. Relative reactivities of benzylbromocarbene toward electron-poor and ...

The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH...

Radical Addition Rate Constants to Acrylates and Oxygen: R-Hydroxy and R-Amino Radicals Produced photolysis of R-hydroxy and R-amino ketones, which are used as photoinitiators in free radical polymerization, lead to the generation of a series of nucleophilic R-hydroxy and R-amino radicals. Absolute addition

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambi...

of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes, Matthias Weber and Nicholas J. Turro values and the alkene concentrations. The validity of the method is demonstrated for the measurement to be applicable to systems with rate constants between 104 and 108 M-1 s-1, a range covered by the alkenes

Absolute rate constants were measured for the gas-phase reactions of the hydroxyl radical with a series of hydrochlorofluorocarbons and hydrofluorocarbons by the flash photolysis-resonance fluorescence technique. These kinetic data, when combined with data obtained independently in other laboratories, lead to the recommended ...

The rate constants for the reactions of atomic bromine with dimethyl ether and diethyl ether were measured from approximately 300 to 350 K using the relative rate method. Both isooctane and isobutane were used as the reference reactants, and the rate constants for the reactions of these ...

The rate constants for the decay of ultraviolet fluorescence from liquid butane, pentane, and hexane have been measured as a function of temperature between their respective freezing points and near-room temperature. The rate constants are well characterized as the sum of an activated and nonactivated term, as has ...

Dichlorocarbene is the cornerstone of singlet carbene reactivity. Moss has thoroughly characterized carbenic selectivity in cyclopropanation reactions. The reactivity of any singlet carbene (:CXY) may be standardized by comparison of its reactivity toward a standard set of alkenes with that of chlorocarbene (:CCl{sub 2}). Amazingly, however, the absolute kinetics of this ...

The interpretation of quantitative relationships between chemical properties and biological effects requires great caution if erroneous conclusions are to be avoided. A knowledge of intracellular concentrations is especially desirable. Since many chemical properties are themselves interrelated, reliable identification of critical reactions may be difficult. Free radicals often react by electron ...

The absolute rates of reaction of tert-butoxy radicals with a variety of organic substrates in solution have been determined using laser flash photolysis techniques. The relative rates agree well with values obtained from studies of hydrocarbon halogenation by tert-butyl hypochlorite or by ESR in the case of ethers and alcohols, while ...

The rates of thermal and photochemical reactions of butyral-dehyde with nitrogen dioxide were measured. A least squares treatment of the data yielded a thermal rate constant of 10 to the 7.4 times base e to the minus 12,400/ (molar gas constant times absolute temperature), where the ...

The kinetics of chemical reactions of cobalt clusters Co{sub n} with deuterium are described. Absolute rate constants have been measured in the cluster range n = 7--68 at 293 K. The rate constants are found to be a strong function of cluster size, varying by up to three orders of magnitude. ...

The kinetics of chemical reactions of cobalt clusters Co{sub n} with deuterium are described. Absolute rate constants have been measured in the cluster range n = 7--68 at 293 K. The rate constants are found to be a strong function of cluster size, varying by up to three orders of magnitude. ...

, College- Educated Population, age 25 to 39 Half-Lifeb Absolute Rate (%)a Iowa 43,206 -11,691 -22.0 13 b years before college-educated population is halved, assuming constant migration rates Inside lifetime earnings, reduced reliance on welfare, and lower crime rates (Institute of Education ...

Using compartmental analysis methods, a mathematical basis is given for the measurement of absolute and fractional cardiac output with diffusible tracers. Cardiac output is shown to be the product of the blood volume and the sum of the rate constants of tracer egress from blood, modified by a factor reflecting transcapillary ...

Previous computation of stability factors of colloidal gold from coagulation data was found to be in systematic error due to an underestimation of the particle concentration by electron microscopy. A new experimental technique was developed for determination of this concentration. Stability factors were recalculated from the previous data using the correct concentration. While most of the ...

The BEPCII Luminosity Monitor (BLM) monitors relative luminosity per bunch. The counting rates of gamma photons, which are proportional to the luminosities from the BLM at the center of mass system energy of the ? (3770) resonance, are obtained with a statistical error of 0.01% and a systematic error of 4.1%. Absolute luminosities are also determined by ...

Absolute rate constants for reaction of .SO/sub 4//sup -/ with substituted benzenes and benzoates have been determined by pulse radiolysis. The values are found to range from about 5 x 10/sup 9/ M/sup -1/ s/sup -1/ for anisole to less than 10/sup 6/ M/sup -1/ s/sup -1/ for nitrobenzene. A correlation of the rate ...

The paper presents the first laboratory measurement of the rate constant for quenching the CO2(0110) state during collisions of CO2 molecules with O atoms at temperatures realized near the Earth's mesopause. The measurement was carried out with a hollow-cathode glow discharge in the temperature range 206-358 K. The measured values are significantly smaller ...

... Title : ABSOLUTE CHEMILUMINESCENT REACTION RATES FOR EMISSION OF THE O2 HERZBERG BANDS IN OXYGEN AND OXYGEN-INERT ...

When analyzing I --> S variable contact time cross-polarization (CP) curves, the spin dynamics are usually assumed to be describable in the "fast CP regime" in which the growth of the S spin magnetization is governed by the rate of cross polarization while its decay is governed by the rate of I spin T1rho relaxation. However, in the investigation of the ...

A pulsed power supply system with constant pulse energy has been developed to drive flashlamps in a 0.5--5 pulses per second Nd : glass laser. By using a stable, absolute reference voltage source to set the trigger level, the energy discharged through the flashlamps is kept constant despite pulsing frequency change, power line ...

The data obtained from radiation chemistry experiments, and, particularly, pulse radiolysis studies that allow absolute rate constants to be obtained, can be of considerable value to investigations in free radical biology. In this article, the authors review leading sources of rate, spectral, and thermodynamic data ...

The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photo...

Stereoscopic vision relies mainly on relative depth differences between objects rather than on their absolute distance in depth from where the eyes fixate. However, relative disparities are computed from absolute disparities, and it is not known where these two stages are represented in the human brain. Using functional MRI (fMRI), we assessed ...

It is shown that Big Bang nucleosynthesis constraints on the mirror Universe are not an absolutely rigorous test.

( + ) where is Boltzman's constant and T is the absolute temperature and derive an equation for the viscosity

Gamma spectral analysis of irradiated material can be used to determine absolute disintegration rates for specific radionuclides. These data, together with measured values for the thermal and epithermal neutron fluxes, and irradiation, cooling and counting time values, are all the experimental information required to do absolute ...

... Rate constants and branching ratios for the dissociative recombination of ... Rate constants and branching ratios for the dissociative recombination ...

May 31, 2011 ... Determination of Chemical Kinetic Rate Constants of a Model for ... product of the surface reaction rate constant ? and the concentration of ...

Laser photolysis-resonance fluorescence at 298 K is used to obtain absolute rate constants for the gas-phase reactions of OH radicals with three trichloroacetaldehydes and acetaldehyde. The rate constants for all but trichloroacetaldehyde are in good agreement with previous literature with the ...

A new similarity solution is obtained for flow of a uniform stream past an aligned, semi-infinite flat plate. The fluid is incompressible, of constant density, and constant absolute viscosity. A detailed examination is made of flows involving steady rates of accretion and of ablation at the leading edge. Both the ...

ABS>By means of the pulse radiolysis technique, a short-lived transient species was observed in irradiated de-aerated ethanol and methanol, exhibiting an optical absorption throughout the visible and near infrared. This transient is suggested to be the solvated electron on the basis of the nature of the spectrum, the reactivity with hydrogen ion and with various organic electron ...

Silicon wafers ((100)-p-type) were abraded at room temperature in acetone, absolute ethanol and water by a pyramid diamond and the resulting groove depth was measured as a function of normal force on the diamond and the absorbed fluids, while all other experimental conditions were held constant. The groove depth rates are in the ratio ...

The effect of intensity on the radioinduced oxidation of deaerated ferrous sulfate solutions was studied using a 1.5-Mev electron beam produced by a Van de Graaff accelerator. The decrease in the yield of Fe(III) with increasing intensity is primarily due to a competition between the combination of hydrogen atoms to produce hydrogen and the oxidation of ferrous ion by hydrogen atoms. ...

Absolute rate constants and degradation efficiencies for hydroxyl radical and hydrated electron reactions with four different sulfa drugs in water have been evaluated using a combination of electron pulse radiolysis/absorption spectroscopy and steady-state radiolysis/high-performance liquid chromatography measurements. For ...

Theory and computation have long been used to rationalize the experimental association rate constants of protein-protein complexes, and Brownian dynamics (BD) simulations, in particular, have been successful in reproducing the relative rate constants of wild-type and mutant protein pairs. Missing from previous BD ...

were obtained with p = +1.4 - 1.6. In the absence of absolute kinetic information, the alkenic with standard sets of alkenes. 1 Hammett analyses generally involved substituent variation on arylalkene sub it possible to determine absolute rate constants for additions to alkenes of carbenes previously studied only

The rates of the various elementary reactions of the type H + H/sub 2/ yields H/sub 2/ + H, involving ortho-para conversions or isotope exchanges, have been calculated by the absolute reaction rate theory, using new fundamental energy surface, but estimating the activation energy to fit experimental results. The transition ...

The absolute rate coefficients and product yields for reactions of O(1D) with HCl(1) and HBr(2) at 287 K are presently determined by means of the time-resolved resonance fluorescence detection of O(3P) and H(2S) in conjunction with pulsed laser photolysis of O3/HX/He mixtures. Total rate coefficients for O(1D) removal are found to be, ...

The decay-rate constant, k, of pyrene anions in 2-methyltetrahydrofuran (MTHF) and in a methylcyclohexane (MCH)-2-methylbutane (2MB) mixture were measured over a wide temperature range of 88-230 K by pulse- and ..gamma..-radiolysis methods. The decay-rate constants could be varied by 9 orders of magnitude. The ...

The absolute rate constant for the reaction H + C4H2 has been measured over the temperature (T) interval 210-423 K, using the technique of flash photolysis-resonance fluorescence. At each of the five temperatures employed, the results were independent of variations in C4H2 concentration, total pressure of Ar or N2, and flash intensity ...

We examine an economy whose consumers have different discount factors for utility, possibly not exponential. We characterize the properties of efficient allocations of resources and of the shadow prices that would decentralize such allocations. We show in particular that the representative agent has a decreasing discount rate when, as is usually posited, all of a group's ...

Compare the graph of a linear function, the graph of an absolute-value function, and the graphs of their translations. Vary the coefficients and constants in the functions and investigate how the graphs change in response.

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO was determined by the flash-photolysis resonance fluorescence method to be 7.5 plus or minus 0.9 (2 sigma) times 10 to the minus 11th power cu cm/molecule sec at 298 K and to have a ne...

The effect of temperature on growth of young-of-the-year yellow perch was determined over an 8-week period at constant temperatures from 8 to 34C. Absolute growth rates peaked at 28C, but were not significantly less (P > 0.05) over the range from 26 to 30...

A careful determination of the absolute reaction rate constants for the vapor phase thermal decomposition of 1-(4'-methoxyphenyl)ethyl acetate and its 3'methyl and 3',5'-dimethyl derivatives provides convincing evidence that P1-orbital overlap of the meth...

The studies use pulse radiolysis to provide absolute rate constants for reactions of many inorganic radicals and organic peroxyl radicals, key intermediates in many chemical processes, and to study electron transfer reactions of metalloporphyrins for sola...

Experiments were performed with a millimeter wave resonance-spectrometer capable of measuring absolute attenuation rates alpha (dB/km) by water vapor up to saturation pressures. Vapor (e) and air (p) pressures were varied at constant temperature and set f...

laser photolysis of DBK (and also DMDBK and TMDBK in Table I) produced a transient absorption at 317 nm which was assigned to the benzyl radical. An initial jump in transient absorption occurred within the time period of the laser pulse and was followed by a measurable first- order growin of absorption. We

Rate constants for the reaction H + H + M - H2 + M, with M = H2, He, and Ar were measured over the temperature range 77 to 298 K. Hydrogen atoms were produced by thermal dissociation and absolute atom concentrations were measured through use of self-balan...

We have used the PIBETA large acceptance pure CsI calorimeter and the stopped pion beam technique to extract a new experimental constraint on the tensor coupling constant in the radiative pion decay ?^+? e^+??. We have measured the absolute decay probability in the kinematic region defined by ...

... Accession Number : AD0630830. Title : RATE CONSTANTS FOR REACTIONS IN THE HYDROGEN-BROMINE SYSTEM,. ...

... Title : CALCULATION OF RECOMBINATION RATE CONSTANTS OF DIATOMIC GASES BY THE MACH NUMBER OF THE STREAM AT THE ...

... Title : ACTIVATION ENERGIES AND RATE CONSTANTS COMPUTED FOR THE COMBUSTION OF HYDROCARBON AND HYDROGEN FUELS,. ...

The production rates of apolipoprotein (apo)B-100 in very low density lipoprotein and in low density lipoprotein and apolipoprotein A-I in high density lipoprotein were determined using a primed-constant infusion of (5,5,5,-2H3)leucine, (4,4,4,-2H3)valine, and (6,6-2H2,1,2-13C2)lysine. The three stable isotope-labeled amino acids were administered ...

The reaction of tert-butoxy radicals with diphenylmethanol and with cumene was examined using nanosecond laser flash photolysis techniques in order to determine the absolute values of the rates of reaction of the radicals. The absolute rate measured for both substrates compare favorably with the values for the ...

f visual cortical response properties. However, it is not only the absolute firing rate that determines how accurately a neuron can signal the presence or character of a particular stimulus. Information in a neuronal response is limited not only by firing rate but also by variability. Presented with the same stimulus on repeated ...

In order to resolve the discrepancies which presently exist between the directly measured values of the absolute or SI ampere and the calculated values obtained indirectly from other fundamental physical constant determinations, one must design an absolut...

Absolute rate constants for the reaction of the hydrated electron and hydroxyl radical with ozone in aqueous solution have been determined by using pulse radiolysis techniques. The rate constant, k(e/sub aq//sup -/ + O/sub 3/) = (3.60 +- 0.14) x 10/sup 10/ dm/sup 3/ mol/sup -1/ s/sup -1/, was ...

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, *OH, and hydrated electron, e(aq)-, reactions were (4.97 +/- ...

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± ...

Rate constants and their temperature dependencies were measured for the chemiluminescent reaction of ozone with the flame and furnace effluents of two commercially available sulfur detectors, the Sulfur Chemiluminescence detector (registered trademark of Sievers Instruments, Inc.) and the Chemiluminescent Sulfur Detector (registered trademark of Antek ...

Namely there are absolute constants Ci > 0 and C2 > 0 such that. Cin log(n + 1) ... C2 log �. 2 i-��. 1-y is also proved with absolute constants Ci > 0 and C2 > 0. ...

where p is gas pressure, V is volume, mu is the number of moles, R is the universal gas constant (= 8.3144 j/(oK mole)), and T is the absolute temperature . ...

Absolute rate constants determined by using the flash photolysis-resonance fluorescence technique are reported for the reactions of hydroxyl radicals with isoprene, ..cap alpha.., and ..beta..-pinene, methyl vinyl ketone, and methacrolein in the temperature range 297-424 K, and with methylglyoxal at 297 K. These results contribute to a ...

The low temperature tensile and creep behaviors of single crystals of Cu were evaluated and analyzed in such a manner as to provide an estimate of the separate contributions of short and long range stress fields to strain-hardening. Furthermore, the average force-displacement diagram for thermally activated intersection of two dislocations were estsblished. This diagram plus a knowledge ...

We have developed hot-wire anemometry applying the 3? method. The approach is based on the same heat transfer process as traditional anemometry, but substituting the constant current by a sinusoidal current and using synchronous detection to measure the conductive-convective exchange coefficient and the gas flow rate. Our theoretical model is tested with ...

The thermal decomposition kinetics of the titled disilanes obtained from static system investigations under conditions of maximum quenching of silylene chains are reported. Single-pulse shock-tube kinetic results on the 1,1,2-trimethyldisilane decomposition as well as relative rate kinetics of silylene insertions into silane and methylsilane at elevated temperatures are also ...

The influence of oxidation temperature on the degree of purification of a model vapor-air mixture (VAM) is shown in terms of removal of isopropylbenzene for coatings based on KO-08 varnish and catalysts AP-64, GIPKh-105-B and STK-1-7. The same influence is shown for removal of isopropylbenzene and n-paraffins on coatings based on KO-08 lacquer and catalysts STK-1-7 and AP-64. The purification ...

... of the reaction rate (defined as the absolute difference between the two reaction rates divided by the rate of photocatalysis alone) imparted by the ...

Measurements of the absolute spectral irradiance from O2(a)-O2-H2O gas, produced by a chemical singlet oxygen generator, were performed. FWHM of singlet oxygen collision induced emission (CIE) at 634 and 703 nm have been measured in the temperature range 150-400 K. The measured rate constant of CIE at 634 nm - (6.72+/-0.8)�10-23 ...

Relative rate experiements were used to measure rate constants and temperature denpendencies of the